Polymerizable biaryls, method for the production and use...

Details Polymerizable biaryls, method for the production and use... Polymerizable biaryls, method for the production and use...

1999-06-09

2001-11-27

Padmanabhan, S (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S426000, C568S441000, C568S442000, C568S630000, C568S715000, C570S182000, C570S183000, C560S056000, C560S064000

Reexamination Certificate

active

06323373

ABSTRACT:

Derivatives of poly(p-phenylenevinylene) have been known for some time as electroluminescence (EL) materials (see, for example, WO-A 90/13148). If the phenylene group in these polymers is substituted by one or more further aryl radicals, EL materials having a very special property spectrum, which are particularly suitable for generating green electroluminescence, are obtained.
Starting compounds for such polymers are biaryl monomers which have two groups capable of polymerization, e.g. CH
2
Br, present on one ring in the 1,4 positions.
In order to be able to prepare polymers having properties which are useful in practice in EL displays, the appropriate monomers are required in extraordinarily high purity. In addition, a requirement of industrial use is that an appropriate purity can be achieved in as few as possible simple and inexpensive steps.
Since, in addition, the development of electroluminescence materials, particularly those based on polymers, can in no way be regarded as concluded, the manufacturers of lighting and display devices are still interested in a wide variety of electroluminescence materials for such devices.
Industrial practice therefore needs, in particular, a broad range of monomers to be able to be prepared by one synthetic method.
The prior art discloses the introduction of groups capable of polymerization into a biaryl by means of electrophilic substitution (cf., for example, G. Subramaniam et al., Synthesis, 1992, 1232 and v. Braun, Chem. Ber. 1937, 70, 979).
However, this route is not generally applicable, since the substitution usually takes place on both aryl systems, which requires at least a complicated separation of the various products.
The bromination of 4,4″-dihexyloxy-2′,5′-dimethyl-p-terphenyl using N-bromosuccinimide has been described by J. Andersch et al., J. Chem. Soc. Commun. 1995, 107. However, bromination occurs here not only on the methyl groups but also one of the alkoxy chains (see Comparative Experiment V2 and K. L. Platt and F. Setiabudi, J. Chem. Soc. Perkin Trans. 1, 1992, 2005).
W. E. Bachmann and N. C. Denno, J. Am. Chem. Soc. 1949, 71, 3062, describe the synthesis of biaryl derivatives by 4+2 cycloaddition of a styrene to a diene-1,6-dicarboxylic acid derivative and subsequent dehydrogenation of the six-membered ring formed to give the aromatic. A disadvantage here is, apart from price and availability of the starting compounds, the fact that the conditions of the dehydrogenation reaction are not tolerated by all functional groups and the substitution pattern is therefore considerably restricted. There was therefore a further need for a general synthetic method which meets the abovementioned requirements. It has now been found that functionalized aryl-1,4-bismethanols and -biscarboxylic esters represent widely and simply accessible starting materials which can easily be converted in high purity into the desired monomers by the specific reaction sequence comprising palladium-catalyzed coupling with a second aryl component and conversion of the alcohol or ester functions into groups suitable for polymerization.
The invention accordingly provides a process for preparing a polymerizable biaryl derivative of the formula (I),
where the symbols and indices have the following meanings:
X: —CH
2
Z, —CHO;
Y
1
, Y
2
, Y
3
: identical or different, CH, N;
Z: identical or different. I, Cl, Br, CN, SCN, NCO, PO(OR
1
)
2
, PO(R
2
)
2
, P(R
3
)
3
+
A
−
;
Aryl: an aryl group having from 4 to 14 carbon atoms;
R′, R″: identical or different, CN, F, Cl, a straight-chain or branched or cyclic alkyl or alkoxy group having from 1 to 20 carbon atoms, where one or more nonadjacent CH
2
groups can also be replaced by —O—, -S-, —CO—, —COO—, —O—CO—, —NR
4
—, —(NR
5
R
6
)
+
—A
−
or —CONR
7
— and one or more H atoms can be replaced by F, or an aryl group having from 4 to 14 carbon atoms which may be substituted by one or more nonaromatic radicals R′;
R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
: identical or different, aliphatic or aromatic hydrocarbon radicals having from 1 to 20 carbon atoms, where R
4
to R
7
can also be hydrogen;
A
⊖
: a singly charged anion or its equivalent;
m: 0, 1 or 2;
n: 1, 2, 3, 4 or 5;
which comprises
A. reacting two aryl derivatives of the formulae (II) and (III),
 in an inert solvent in the presence of a palladium catalyst at a temperature in the range from 0° C. to 200° C. to give an intermediate of the formula (IV)
where the symbols and indices have the meanings given in formula (I) and X′: CH
2
OH or COOR
8
; one of the groups T, T′: Cl, Br, I or a perfluoroalkylsulfonate radical, preferably having from 1 to 12 carbon atoms, and the other group T, T′: SnR
3
, BQ
1
Q
2
, where
Q
1
,Q
2
are identical or different and are each —OH, C
1
-C
4
-alkoxy, C
1
-C
4
-alkyl, phenyl which may bear C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy or halogen groups as substitutents, or halogen or Q
1
and Q
2
together form a C
1
-C
4
-alkylenedioxy group which may be substituted by one or two C
1
-C
4
-alkyl groups; and
R
8
are identical or different and are each H or a straight-chain or branched alkyl group having from 1 to 12 carbon atoms;
B. if the group X′ in the intermediate of the formula (IV) is COOR
8
(IVa), reducing this by means of a reducing agent to give an intermediate of the formula (IV) in which X′ is CH
2
OH (IVb), and
C. reacting the resulting intermediate of the formula (IVb) according to one of the following reactions:
a) selective oxidation to form a compound of the formula (I) where X=CHO or
b) replacement of the OH group by a halogen or pseudohalogen by means of nucleophilic substitution to form a compound of the formula (I) where Z=Cl, Br, I, CN, SCN, OCN; and
D. if desired, converting compounds of the formula (I) where Z=Cl, Br, I into a biaryl derivative of the formula (I) where Z=PO(OR
1
)
2
, PO(R
2
)
2
, P(R
3
)
3
+
A
−
by reaction with the corresponding organophosphorus compounds.
A significant advantage of the process of the present invention is that the biaryl derivatives can generally be purified in a simple manner, in particular by recrystallization.
Although most compounds of the formula (IV) where X′=COOR and of the formula (I) where X=CH
2
Cl, CH
2
Br are high-boiling oils, they can generally be obtained in pure form from the synthesis. The coupling reactions selected according to the invention can routinely be carried out such that the resulting products (IV) are obtained in purities of greater than 90% The reaction to form bishalides of the formula (I) generally leads only to low by-product formation, so that these substances are obtained in a purity similar to that of the bisalcohols (IV) used. These in turn are generally crystalline substances which can readily be purified to purities of greater than 99% by simple recrystallization. The same applies to the bisphosphonates and, in particular, bisphosphonium salts of the formula (I). In the case of the bisaldehydes of the formula (I), a highly viscous oil or a crystalline substance is obtained depending on the substitution pattern. If the reaction conditions in the preparation are chosen according to the invention (e.g. Swern oxidation), the bisaldehyde is likewise obtained in high purity directly from the reaction mixture.
The process of the invention is depicted in Scheme 1.
The starting compounds of the formulae (II) and (III) are very readily obtainable, since some of them are commercially available, e.g. bromoterephthalic acid, or they can be prepared in a simple manner and in large amounts from commercially available compounds.
The following may be said about the reactions in Scheme 2: the 1,4-dimethyl compound (V) is generally commercially available (e.g. p-xylene, 2,5-dimethylphenol, 2,5-dimethylaniline, 2,5-dimethylbenzonitrile, 2,5-dimethylpyridine) or is simple to prepare from commercially available compounds (e.g. alkylation of a corresponding phenol or amine), compound (V) can be

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